CN108232205A - Base metal class catalyst and its manufacturing method - Google Patents

Base metal class catalyst and its manufacturing method Download PDF

Info

Publication number
CN108232205A
CN108232205A CN201710744032.6A CN201710744032A CN108232205A CN 108232205 A CN108232205 A CN 108232205A CN 201710744032 A CN201710744032 A CN 201710744032A CN 108232205 A CN108232205 A CN 108232205A
Authority
CN
China
Prior art keywords
base metal
class catalyst
metal class
phenanthroline
tetramethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710744032.6A
Other languages
Chinese (zh)
Other versions
CN108232205B (en
Inventor
李株熙
金元中
李成圭
李镇宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hyundai Motor Co
Academy Industry Foundation of POSTECH
Kia Corp
Original Assignee
Hyundai Motor Co
Kia Motors Corp
Academy Industry Foundation of POSTECH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hyundai Motor Co, Kia Motors Corp, Academy Industry Foundation of POSTECH filed Critical Hyundai Motor Co
Publication of CN108232205A publication Critical patent/CN108232205A/en
Application granted granted Critical
Publication of CN108232205B publication Critical patent/CN108232205B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • B01J35/647—
    • B01J35/651—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to base metal class catalyst and its manufacturing methods.Embodiment of the present invention is related to base metal class catalyst and its manufacturing method as fuel cell electrode material.In one aspect of the invention, there is provided herein a kind of base metal class catalyst for fuel cell electrode.The base metal class catalyst includes the porous carbon with the first hole and second hole smaller than the first hole.First hole is with about 5 to 100nm aperture and with the inner wall for the active site for introducing base metal class catalyst.

Description

Base metal class catalyst and its manufacturing method
Technical field
The present invention relates to base metal class catalyst and its manufacturing method as fuel cell electrode material.
Background technology
In conventional Proton Exchange Membrane Fuel Cells (PEMFC), it is widely used including with high catalytic activity and height electricity The noble metal (particularly platinum) of gesture makees fine grained as main component as electrode catalyst.
However, since platinum is the rare metal of high cost, exploitation is used for the oxygen reduction reaction of fuel cell, has height The demand of alternative base metal class catalyst that is active and substituting platinum catalyst is growing day by day.
It has studied using the additive of such as zirconium oxide to reduce the method used of platinum.It has been reported that by splashing It penetrates and the nitrogen oxides of transition metal is attached to the surface of carrier material to manufacture transition metal oxynitrides electrode catalyst Method.
However, currently available base metal class electrode catalyst has catalytic activity unsatisfactory, therefore can To improve the performance for the fuel cell for including base metal class electrode catalyst.
The information for being disclosed in the background of invention technology segment is merely intended to deepen the reason of the general background technology to the present invention Solution, and be not construed as recognizing or to imply that the information is formed in any form known to those skilled in the art existing Technology.
Invention content
Various aspects of the invention are related to providing with the active site being selectively positioned on micropore surface Base metal class catalyst and its manufacturing method.In accordance with an exemplary embodiment of the invention, it is possible thereby to control to manufacture The type and its machined parameters of the base metal class catalyst precarsor of base metal class catalyst.
Other aspects of the disclosure will be set forth in part in the description, and partly will be aobvious and easy from description See or can be understood by the practice of the disclosure.
In one aspect of the invention, a kind of base metal class catalyst for fuel cell electrode is provided.It is non-expensive Metal-based catalysts include the porous carbon with the first hole and second hole smaller than the first hole, and the first hole has about 5 to 100nm's Aperture (for example, about 5nm, 10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95 or about 100nm) and with the inner wall for the active site for introducing base metal class catalyst.
Porous carbon can have the structure that the first hole and the second hole uniformly connect in three dimensions.
First hole can with about 15 to 60nm aperture (for example, about 15,16,17,18,19,20,21,22,23,24, 25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、 50th, 51,52,53,54,55,56,57,58,59 or about 60nm).
The active site of base metal class catalyst can be provided in the form of being represented by following formula 1：
Formula 1
MxNy
Wherein x is 0 to 1 integer, and y is 1 to 4 integer, and M is transition metal.
The active site of base metal class catalyst can be formed by base metal class catalyst precarsor.
Base metal class catalyst precarsor can have wherein at least one of following form with metal coordination：Phthalein Cyanines, phthalocyanine tetrasulfonate, eight butoxy phthalocyanines, ten hexafluoro phthalocyanines, eight octyloxy phthalocyanines, tetra-tert phthalocyanine, four azepine phthalocyanines, Four phenoxy group phthalocyanines, four-dimethylamino of tetra-tert phthalocyanine, four cumylphenoxy phthalocyanines, four pyrido methyl phthalocyanines, tetranitro Phthalocyanine, naphthalene phthalocyanine, tetra-tert naphthalene phthalocyanine, tetraphenylporphines, four pentafluorophenyl group porphyrins, tetramethyl pyridine and porphyrin durene sulphur Hydrochlorate, four-trimethylamino phenyl porphyrin tetramethyl benzene sulfonate, tetramethyl divinyl porphines dipropionic acid, four pyridyl group porphines, Octaethylporphyrin, tetramethoxy phenyl porphine, tetraphenylporphines tetrabasic carboxylic acid, tetrahydroxy phenyl porphine, tetrasulfonic acid root close phenyl porphin Fen, etioporphyrin (ETIO), 1,10- phenanthroline, 1,10- phenanthroline -5,6- diketone dimethyl -1,10- phenanthroline, dimethyl -1,10- phenanthrene are coughed up Quinoline, dimethoxy -1,10- phenanthroline, amino -1,10- phenanthroline, methyl-1,10- phenanthroline, dihydroxy -1,10- phenanthroline, Tetramethyl -1,10- phenanthroline, chloro- 1,10- phenanthroline, two chloro- 1,10- phenanthroline, nitro -1,10- phenanthroline, bromo- 1,10- Phenanthroline, four bromo- 1,10- phenanthroline, pyrazine simultaneously [1,10] phenanthroline, diphenyl -1,10- phenanthroline, dimethyl diphenyl -1, 10- phenanthroline, two propoxy- of ethylidine formoxyl (hydroxyl trimethyl tetradecyl base) trimethyl porphines, diethylene tetramethyl Two propoxy- of porphines, bis- two propoxy-s of ((amino carboxyethyl) is thio) ethyl tetramethyl porphines, dihydro dihydroxy tetramethyl Divinyl porphines dipropyl acid lactone, two propoxy- of ethylidine (14 carbon trialkenyl of hydroxyl trimethyl) tetramethyl porphines, carboxylic Bis- (methylol) the tetramethyl porphines dicarboxylic acids compounds of base ethylidine carboxyethyl dihydro, (dimethylbenzimidazole base) cyanocobalamin acyl The big ring of amine, Ke Disi,Big ring and the big rings of DOTA.
Metal can include at least one transition gold selected from iron (Fe), cobalt (Co), manganese (Mn), nickel (Ni) and chromium (Cr) Belong to.
Total weight based on porous carbon, base metal class catalyst precarsor can be about 1 to 50 weight % (examples comprising weight Such as, about 1 weight %, 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25, 26th, 27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49 or about 50 Weight %) transition metal.
Porous carbon can have the anchored site for the hole surface for introducing porous carbon, be urged with enhancing porous carbon and base metal class Interaction between agent precursor.
According to another aspect of the present invention, a kind of base metal class catalyst manufactured for fuel cell electrode is provided Method.This method can include mixing porous carbon with base metal class catalyst precarsor；About 600 to 1200 DEG C (such as About 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C or about 1200 DEG C) At a temperature of mixture is heat-treated；Thermally treated mixture is stirred in an acidic solution；And washing and drying are agitated Mixture.
Porous carbon can have the first hole and second hole smaller than the first hole, and be catalyzed in porous carbon and base metal class In the mixing of agent precursor, the aperture in the first hole is 5 to 100nm.
First hole can with about 15 to 60nm aperture (for example, about 15,16,17,18,19,20,21,22,23,24, 25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、 50th, 51,52,53,54,55,56,57,58,59 or about 60nm).
This method may further include about 600 DEG C to about 1200 DEG C (for example, about 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C or about 1200 DEG C) at a temperature of in ammonia (NH3) in gas atmosphere After drying, by the solid powder of acquisition be heat-treated about 5 to 60 minutes (for example, about 5 minutes, 10,15,20,25,30,35, 40th, 45,50,55 or about 60 minutes).
This method may further include by about 600 DEG C to about 1200 DEG C (for example, about 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C or about 1200 DEG C) at a temperature of in ammonia (NH3) gas atmosphere Middle heat treatment porous carbon (for example, about 5 minutes, 10,15,20,25,30,35,40,45,50,55 or about 60 points about 5 to 60 minutes Clock) and form anchored site on the hole surface of porous carbon.
In the mixing of porous carbon and base metal class catalyst precarsor, base metal class catalyst precarsor can have it In at least one of the following form with metal coordination：Phthalocyanine, phthalocyanine tetrasulfonate, eight butoxy phthalocyanines, ten hexafluoro phthalocyanines, Eight octyloxy phthalocyanines, tetra-tert phthalocyanine, four azepine phthalocyanines, four phenoxy group phthalocyanines, four-dimethylamino of tetra-tert phthalocyanine, four Cumylphenoxy phthalocyanine, four pyrido methyl phthalocyanines, tetranitro phthalocyanine, naphthalene phthalocyanine, tetra-tert naphthalene phthalocyanine, tetraphenylporphines, Four pentafluorophenyl group porphyrins, tetramethyl pyridine and porphyrin tetramethyl benzene sulfonate, four-trimethylamino phenyl porphyrin tetramethyl benzene sulfonic acid Salt, tetramethyl divinyl porphines dipropionic acid, four pyridyl group porphines, octaethylporphyrin, tetramethoxy phenyl porphine, tetraphenyl porphin Fen tetrabasic carboxylic acid, tetrahydroxy phenyl porphine, tetrasulfonic acid root close phenyl porphine, etioporphyrin (ETIO), 1,10- phenanthroline, 1,10- phenanthroline -5, 6- diketone dimethyl -1,10- phenanthroline, dimethyl -1,10- phenanthroline, dimethoxy -1,10- phenanthroline, amino -1,10- are luxuriant and rich with fragrance Cough up quinoline, methyl-1,10- phenanthroline, dihydroxy -1,10- phenanthroline, tetramethyl -1,10- phenanthroline, chloro- 1,10- phenanthroline, two Chloro- 1,10- phenanthroline, nitro -1,10- phenanthroline, bromo- 1,10- phenanthroline, four bromo- 1,10- phenanthroline, pyrazine are simultaneously [1,10] Phenanthroline, diphenyl -1,10- phenanthroline, dimethyl diphenyl -1,10- phenanthroline, ethylidine formoxyl (hydroxyl trimethyl ten Tetraalkyl) two propoxy- of trimethyl porphines, two propoxy- of diethylene tetramethyl porphines, bis- ((amino carboxyethyl) is thio) Two propoxy- of ethyl tetramethyl porphines, dihydro dihydroxy tetramethyl divinyl porphines dipropyl acid lactone, ethylidine (hydroxyl three 14 carbon trialkenyl of methyl) two propoxy- of tetramethyl porphines, bis- (methylol) the tetramethyl porphins of carboxyl ethylidine carboxyethyl dihydro Fen dicarboxylic acids compound, (dimethylbenzimidazole base) cyanocobalamin amide, the big rings of Ke Disi,Big ring and the big rings of DOTA.
Metal can include at least one transition gold selected from iron (Fe), cobalt (Co), manganese (Mn), nickel (Ni) and chromium (Cr) Belong to.
In the mixing of porous carbon and base metal class catalyst precarsor, the total weight based on porous carbon, base metal class Catalyst precarsor can include the transition metal of 1 to 50 weight %.
Mixture can be included in inert gas atmosphere in the heat treatment at a temperature of 600 to 1200 DEG C 600 to 1200 The heat treatment of 10 to 300 minutes is carried out at a temperature of DEG C to mixture.
Stirring thermally treated mixture in an acidic solution can include adding in thermally treated mixture to concentration For in 0.1M or higher acid solutions and stir gained mixture.
Description of the drawings
Fig. 1 is the schematic cross-section according to the base metal class catalyst for fuel cell electrode of embodiment Figure.
Fig. 2 is the enlarged drawing of part A in Fig. 1.
Fig. 3 is transmission electron microscope (TEM) image of the structure of MSUFC porous carbons.
Fig. 4 is the figure of the pore-size distribution for the micropore for representing MSUFC porous carbons.
Fig. 5 is the figure of the pore-size distribution in the ultra-fine hole for representing MSUFC porous carbons.
Fig. 6 is the TEM image of the structure of final base metal class catalyst.
Fig. 7 is the figure of the pore-size distribution for the micropore for representing base metal class catalyst.
Fig. 8 is the figure for being shown schematically in the reaction occurred on the hole surface for the porous carbon for being not introduced into anchored site.
Fig. 9 is to be shown schematically in the figure of reaction occurred on the hole surface for the porous carbon for introducing anchored site.
Figure 10 is the schematic diagram for representing to manufacture the method for the base metal class catalyst according to embodiment.
Figure 11 is the flow chart for illustrating the method for manufacturing base metal class catalyst.
Figure 12 is the figure for representing oxygen reduction reaction (ORR) result relative to the type of base metal class catalyst precarsor.
Figure 13 is to represent to show the figure for the result for depending on the oxygen reduction reaction (ORR) that anchored site introduces.
Figure 14 is the figure for representing the ORR results relative to heat treatment condition.
Figure 15 and Figure 16 is the figure for representing Koutecky-Levich curves.
Figure 17 is the figure for the performance change for representing the monocell relative to spraying method.
Figure 18 is represented relative to added to the Nafion ionomers in catalyst solution and base metal class catalyst Mass ratio, the figure of the performance change of monocell.
Figure 19 is the figure of the performance change for the monocell for representing the load capacity relative to catalyst.
Figure 20 is the figure for the durability test result for representing monocell.
Figure 21 is the figure for the reaction for representing the reactant according to active site position.
Figure 22 and Figure 23 is represented relative to the ORR results of active site position and the performance change of monocell Figure.
It will be appreciated that attached drawing has not necessarily been drawn to scale, it illustrates in a way by the present invention's that simplifies Each feature of basic principle.The specific design feature of the present invention disclosed herein including such as certain size, is determined To, location and shape, will partly be determined by the application of specific purpose and use environment.
In these figures, reference numeral refers to the same or equivalent of the present invention in several figures through attached drawing Component.
Specific embodiment
The each embodiment that will refer to the present invention in detail now, the example of these embodiments show in the accompanying drawings and retouch It states as follows.Although the present invention will be combined with exemplary implementation and be described, but it is to be understood that this specification is not intended to Limit the invention to those exemplary implementations.On the contrary, the present invention is directed to not only cover these exemplary implementations, and And covering can be included in various selection forms within the spirit and scope of the present invention being defined by the appended claims, Modification, equivalent form and other embodiments.
It is further understood that term " comprising " or " having " are intended to indicate that the presence of the element disclosed in specification, and It is not intended to the possibility that excludes there may be or can add one or more of the other element.
In the present specification, term " first ", " second " etc. are for distinguishing a component and other assemblies, therefore component is not It is limited by term.
The expression way that odd number uses includes the expression of plural form, unless having visibly different contain within a context Justice.
The reference numeral used in operation is not intended to the sequence of description operation for describing conveniently, and unless It is otherwise noted, operation can be executed in different order.
The present invention relates to nanoporous base metal class catalyst and its manufacturing method with homogeneous texture.
Base metal class catalyst in accordance with an exemplary embodiment of the invention is used in Proton Exchange Membrane Fuel Cells (PEMFC) oxygen reduction reaction occurred in cathode.Base metal class catalyst can be by will be before base metal class catalyst Body is doped into have in eurypyloue carbon complex on its surface and be prepared.Therefore, it compared with traditional platinum catalyst, can drop Low manufacture cost, and the base metal class catalyst with tens nanometer grade hole can be reduced in membrane electrode assembly (MEA) Resistance to mass tranfer.
Hereinafter, will the base metal class catalyst for fuel cell electrode according to exemplary implementation be described Structure, then its manufacturing method is described.
Fig. 1 is the schematic cross-section according to the base metal class catalyst for fuel cell electrode of embodiment Figure.Fig. 2 is the enlarged drawing of part A in Fig. 1.
Referring to Figures 1 and 2, it is had a structure in which for the base metal class catalyst of fuel cell electrode, wherein non- The active site of precious metal based catalysts is introduced into the inner wall in the hole of porous carbon.
Although the platinum catalyst load used in general fuel cell electrode is on a surface of the carbon, according to exemplary reality The base metal class catalyst of scheme is applied by the way that base metal class catalyst precarsor to be doped into porous carbon structure to be formed, is changed Yan Zhi, by the way that base metal class catalyst precarsor to be introduced in the carbon web frame of porous carbon to be formed.
As porous carbon, porous carbon materials with hole can be used.The hole of porous carbon surface can include the first hole and Second hole smaller than the first hole.More particularly, the first hole of porous carbon can with about 5 to 100nm aperture (for example, about 5nm, 10th, 15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95 or about 100nm), preferably 15 to 50nm (for example, about 5nm, 6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28, 29th, 30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49 or about 50nm).Second Hole can have the aperture of number nm, be the minimum-value aperture obtained during porous carbon is prepared.Throughout the specification, One hole can be referred to as micropore, and the second hole can be referred to as ultra-fine hole.
First hole and the second hole can form the structure uniformly connected in three dimensions.Hereinafter, it will be based on herein Used MSUFC porous carbons describe the structure of porous carbon and pore size distribution data.
Fig. 3 is transmission electron microscope (TEM) image of MSUFC porous carbon structures, BET surface area：930m2/g.Fig. 4 It is the figure of the pore-size distribution for the micropore for representing MSUFC porous carbons.Fig. 5 is the pore-size distribution in the ultra-fine hole for representing MSUFC porous carbons Figure.
With reference to Fig. 3 and Fig. 4, it was demonstrated that the micropore that aperture is about 15 to about 60nm is formed on the surface of MSUFC porous carbons, and And the channel that size is about 2 to about 10nm is formed wherein.In addition, with reference to Fig. 3 and Fig. 5, it was demonstrated that on the surface of MSUFC porous carbons It is upper to form the ultra-fine hole that aperture is about 0.5 to about 1.5nm.
In general, if the aperture of porous carbon is less than 15nm, resistance to mass tranfer may increase.If the aperture of porous carbon is more than 60nm, then the specific surface area of porous carbon may be decreased.Therefore, have about 5 to 100nm apertures the first hole (for example, about 5nm, 10, 15th, 20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95 or about 100nm), preferably 5 to 60nm (examples Such as, about 5nm, 6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、54、 55th, 56,57,58,59 or about 60nm) it can be introduced into the carbon structure according to exemplary implementation to obtain satisfactorily Resistance to mass tranfer and specific surface area.
As shown in figure 3, the active site of base metal class catalyst is formed on the inner wall in the first hole of porous carbon.It is non-expensive The active site of metal-based catalysts can be by using base metal class catalyst precarsor to be formed.It, can be with according to the present embodiment It is less than the first bore dia and more than the base metal class catalyst precarsor of the second bore dia using diameter, to control manufacturing process Condition so that the active site of base metal class catalyst is formed selectively on the surface in the first hole.
If for example, using the FePC of diameter about 1.2nm as base metal class catalyst precarsor, most of second Hole is less than base metal class catalyst precarsor, therefore most base metal class catalyst precarsor can be with the table in the first hole Face interacts to be formed selectively active site on the inner wall in the first hole.Simultaneously as the channel of porous carbon is such as There is about 2 to about 10nm size, active site can also be formed on the inner wall of channel described in upper.
Fig. 6 is the TEM image of final base metal class catalyst structure, BET surface area：954m2/g.Fig. 7 is to represent The figure of the pore-size distribution of the micropore of base metal class catalyst.Fig. 6 and Fig. 7, which is shown, is using FePC as base metal class Experimental result in the case of catalyst precarsor.
Fig. 6 and result shown in fig. 7 are compared with Fig. 3 and result shown in Fig. 4.It is adulterated according to wherein porous carbon In the case of the base metal class catalyst for having the exemplary implementation of base metal class catalyst precarsor, it can be verified that more Hole carbon is reduced doped with the distribution of the metapore of base metal class catalyst precarsor.Therefore, it can be verified that base metal class catalyst Precursor is doped into the surface of channel design, and forms the first hole and the active site of porous carbon.
Base metal class catalyst precarsor can have wherein at least one of following form with metallic ion coordination： Phthalocyanine, phthalocyanine tetrasulfonate, eight butoxy phthalocyanines, ten hexafluoro phthalocyanines, eight octyloxy phthalocyanines, tetra-tert phthalocyanine, four azepine phthaleins Cyanines, four phenoxy group phthalocyanines, four-dimethylamino of tetra-tert phthalocyanine, four cumylphenoxy phthalocyanines, four pyrido methyl phthalocyanines, four Nitro phthalocyanine, naphthalene phthalocyanine, tetra-tert naphthalene phthalocyanine, tetraphenylporphines, four pentafluorophenyl group porphyrins, tetramethyl pyridine and porphyrin tetramethyl Benzene sulfonate, four-trimethylamino phenyl porphyrin tetramethyl benzene sulfonate, tetramethyl divinyl porphines dipropionic acid, four pyridyl groups Porphines, octaethylporphyrin, tetramethoxy phenyl porphine, tetraphenylporphines tetrabasic carboxylic acid, tetrahydroxy phenyl porphine, tetrasulfonic acid root close benzene Base porphines, etioporphyrin (ETIO), 1,10- phenanthroline, 1,10- phenanthroline -5,6- diketone dimethyl -1,10- phenanthroline, dimethyl -1,10- Phenanthroline, dimethoxy -1,10- phenanthroline, amino -1,10- phenanthroline, methyl-1,10- phenanthroline, dihydroxy -1,10- are luxuriant and rich with fragrance Cough up quinoline, tetramethyl -1,10- phenanthroline, chloro- 1,10- phenanthroline, two chloro- 1,10- phenanthroline, nitro -1,10- phenanthroline, bromo- 1,10- phenanthroline, four bromo- 1,10- phenanthroline, pyrazine simultaneously [1,10] phenanthroline, diphenyl -1,10- phenanthroline, dimethyl hexichol Base -1,10- phenanthroline, two propoxy- of ethylidine formoxyl (hydroxyl trimethyl tetradecyl base) trimethyl porphines, diethylene Two propoxy- of tetramethyl porphines, bis- two propoxy-s of ((amino carboxyethyl) is thio) ethyl tetramethyl porphines, dihydro dihydroxy Tetramethyl divinyl porphines dipropyl acid lactone, ethylidine (14 carbon trialkenyl of hydroxyl trimethyl) tetramethyl porphines two are propylated Bis- (methylol) the tetramethyl porphines dicarboxylic acids compounds of object, carboxyl ethylidine carboxyethyl dihydro, (dimethylbenzimidazole base) cyanogen cobalt The big ring of amine amide, Ke Disi,Big ring and the big rings of DOTA.In this case, metal can be included selected from iron (Fe), cobalt (Co), at least one transition metal of manganese (Mn), nickel (Ni) and chromium (Cr).
Meanwhile the type of base metal class catalyst precarsor is without being limited thereto, can also be construed broadly to include in ability Change in the apparent range of domain those of ordinary skill.
Total weight based on porous carbon, base metal class catalyst precarsor can cause transition metal including transition metal Weight range be about 1 to 50 weight % (for example, about 1 weight %, 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16, 17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、 42nd, 43,44,45,46,47,48,49 or about 50 weight %).
If the weight of transition metal is less than 1 weight % relative to the total weight of porous carbon, may inadequately be formed Active site.If total weight of the weight of transition metal based on porous carbon is more than 50 weight %, all base metals Class catalyst precarsor cannot all enter the first hole of porous carbon, and on the surface of porous carbon.It is porous therefore, it is necessary to be based on The weight of the total weight adjustment transition metal of carbon.
Meanwhile according to exemplary implementation, porous carbon can have the anchored site for the hole surface for introducing porous carbon, with Enhance the interaction between porous carbon and base metal class catalyst precarsor.Anchored site is introduced to the hole surface of porous carbon Process is mixed before being included in the surface with base metal class catalyst precarsor doping porous carbon with nitrogen-atoms in various ways The surface of miscellaneous porous carbon.
Hereinafter, describe to be introduced into or be not introduced into when anchored site the catalysis during hole surface of porous carbon with reference to the accompanying drawings The probability that active site is formed.
Fig. 8 is the figure for being shown schematically in the reaction occurred on the hole surface for the porous carbon for being not introduced into anchored site.Fig. 9 It is to be shown schematically in the figure of reaction occurred on the hole surface for the porous carbon for introducing anchored site.
With reference to figure 8, if not forming anchored site on the hole surface CS of porous carbon, the carbon particle on hole surface CS Interaction between base metal class catalyst precarsor CP is weaker, therefore the probability that active site is formed reduces. In this case, transition metal particles MP can form a period of time on the hole surface CS of porous carbon.Transition metal particles MP It can be eluted by acid solution, this will be described later.
With reference to Fig. 9, if forming anchored site AN on the hole surface CS of porous carbon, anchored site AN can enhance hole The interaction between carbon particle and base metal class catalyst precarsor CP on surface C S.It in other words, can be by using mixing It is miscellaneous enter porous carbon hole surface CS in nitrogen-atoms enhance carbon particle and base metal class catalyst as anchored site AN before Interaction between body CP, to prevent the agglomeration of base metal class catalyst precarsor CP.Furthermore, it is possible to increase catalytic active site The formation of point A is to increase the catalytic activity of base metal class catalyst.
The active site A of base metal class catalyst formed by base metal class catalyst precarsor and anchored site can be with It is represented by following formula 1.
Formula 1
MxNy
In formula 1, x be 0 to 1 integer, y be 1 to 4 integer, M for transition metal such as iron (Fe), cobalt (Co), manganese (Mn), Nickel (Ni) and chromium (Cr).
The base metal class catalyst for fuel cell electrode according to exemplary implementation is described above Structure.Hereinafter, the method that manufacture base metal class catalyst will be described.
Figure 10 is the schematic diagram for illustrating to manufacture the method for the base metal class catalyst according to embodiment.Figure 11 is to be used for Illustrate the flow chart of the method for manufacture base metal class catalyst.
With reference to Figure 10 and Figure 11, manufacture that include according to the method for exemplary implementation base metal class catalyst will be porous Carbon mixes (110) with base metal class catalyst precarsor, and thermally treated mixture (120) stirs thermally treated in an acidic solution Mixture (130) and wash and dry agitated mixture (140).
First, the mixing of porous carbon and base metal class catalyst precarsor include preparing porous carbon and by porous carbon with it is non-expensive Metal-based catalysts precursor mixes.
Porous carbon prepares the process that can include synthesis MSUFC.The process for synthesizing MSUFC is as follows.
First, 9mL furfuryl alcohols are mixed with 6g AIMSUF-Si, while primary a small amount of addition furfuryl alcohol, and by mixture true It is kept for 30 minutes at room temperature in the air.Then, vacuum state is kept for 8 hours in 85 DEG C of baking oven.Then, consolidate what is obtained Body powder is carbonized 2 hours in inert gas atmosphere at 850 DEG C.By the way that temperature is warming up to 600 DEG C with the rate of 1 DEG C/min Then 850 DEG C are warming up to the rate of 5 DEG C/min to be carbonized.Then, the solid powder through carbonization is added in the hydrogen-oxygen of 2M Change sodium (NaOH) solution in, by mixture at 80 DEG C in boiling water heating stirring 6 hours.Then, the mixture of gained is existed It is washed with distilled water under decompression until gains have neutral pH and dry acquisition MSUFC.
However, the above method is the example for synthesizing MSUFC, therefore those skilled in the art can also be used obvious Any other method.
After the completion of MSUFC synthesis, porous carbon and base metal class catalyst precarsor are mixed.
The obtainable base metal class catalyst in the mixed process of porous carbon and base metal class catalyst precarsor Type is as described above.In this respect, the activity of oxygen reduction reaction depends on the type of base metal class catalyst precarsor.Below In, will the experimental result of oxygen reduction reaction activity that tested according to base metal class catalyst precarsor be described, so as to more preferable geographical Solution.
Figure 12 is the result for representing the oxygen reduction reaction (ORR) relative to the type of base metal class catalyst precarsor Figure.
Figure 12 is shown using 0.5M oxygen saturation sulfuric acid (H2SO4) solution, load capacity is 815 μ g/cm2Base metal class Catalyst and load capacity are 16 μ gpt/cm2The ORR of the first to the 5th sample that measure at 1600 rpm of 40 weight %Pt/C As a result.
In this respect, the first sample is that FePC is used to be catalyzed as the base metal class of base metal class catalyst precarsor Agent sample, the second sample are the base metal class catalyst samples for using phenanthroline iron as base metal class catalyst precarsor, Third sample is the base metal class catalyst sample for using vitamin B12 as base metal class catalyst precarsor, the 4th sample Product are using 5,10,15,20- tetra- (4- methoxyphenyls) -21H, and 23H- porphines iron chloride (III) is catalyzed as base metal class The base metal class catalyst of agent precursor, the 5th sample are that wherein platinum (Pt) is supported on the supported catalyst on carbon.
As analyzed based on the curve graph of Figure 12 in -3mA/cm2Lower measurement it is half wave potential as a result, the 5th sample can be confirmed Product have highest half wave potential, and half wave potential is with the sequence of the 4th sample, the first sample, third sample and the second sample It reduces.With the increase of half wave potential, catalytic activity increases.Therefore, can be confirmed is had using the 5th sample of platinum catalyst Highest catalytic activity.
It is also possible to confirm that the half wave potential of first to fourth sample using base metal class catalyst precarsor is slightly lower In the half wave potential of the 5th sample.Therefore, it can be confirmed using before the base metal class catalyst with the manufacture cost reduced Body can obtain the base metal class catalyst with relatively excellent catalytic activity.
Meanwhile the amount of base metal class catalyst precarsor can be adjusted so that be catalyzed based on porous carbon and base metal class The total weight of porous carbon in the mixing of agent precursor, the amount of contained transition metal is in about 1-50 in base metal class catalyst precarsor In the range of weight % (for example, about 1 weight %, 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19, 20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、 45th, 46,47,48,49 or about 50 weight %).Added to the weight range of the transition metal in porous carbon meaning as described above, And details are not described herein.
According to exemplary implementation, the mixing of porous carbon and base metal class catalyst precarsor can be included positioning of anchor Point introduces porous carbon.The process can be carried out to enhance the interaction between porous carbon and base metal class catalyst precarsor. However, it is possible to omit the process.
Figure 13 is the figure of oxygen reduction reaction (ORR) result for representing the introducing depending on anchored site.
Figure 13 is shown using 0.5M oxygen saturation sulfuric acid (H2SO4) solution, load capacity is 815 μ g/cm2Base metal class Catalyst and load capacity are 16 μ g pt/cm2The ORR of the 6th to the 9th sample that measure at 1600 rpm of 40 weight %Pt/C As a result.
In this respect, the 6th sample is to use 5,10,15,20- tetra- (4- methoxyphenyls) -21H, 23H- porphines iron chloride (III) as the base metal class catalyst sample of base metal class catalyst precarsor, the 7th sample is drawn by anchored site After entering into porous carbon, using FePC as the base metal class catalyst sample of base metal class catalyst precarsor, Eight samples are to use 5,10,15,20- tetra- (4- methoxyphenyls) -21H, 23H- after anchored site is introduced in porous carbon Base metal class catalyst sample of the porphines iron chloride (III) as base metal class catalyst precarsor, the 9th sample is wherein Platinum (Pt) is supported on the supported catalyst on carbon.
As analyzed based on the curve graph of Figure 13 in -3mA/cm2Lower measurement it is half wave potential as a result, the 7th sample can be confirmed Product have highest half wave potential, and half wave potential is reduced with the sequence of the 8th sample, the 9th sample, the 6th sample.Especially By comparing the 6th sample and the 8th sample, the 8th sample with the anchored site that porous carbon is introduced using nitrogen can be confirmed in ground Product are with the 6th sample than no anchored site with higher catalytic activity.Further, since the 7th and the 8th sample is urged Change the catalytic activity for the 9th sample that activity is higher than using noble metal catalyst, can be confirmed can be to prevent by introducing anchored site Only use the reduction of catalytic activity caused by base metal class catalyst.
After porous carbon is mixed with base metal class catalyst precarsor, which can be heat-treated.
The heat treatment of mixture can by inert gas atmosphere at a temperature of 600 to 1200 DEG C to mixture into The row heat treatment of about 10 to 300 minutes carries out.Herein, the type of inert gas can include argon (Ar), nitrogen (N2), helium (He) With neon (Ne), but it is not limited to this.
If heat treatment temperature is less than 600 DEG C, active site is not effectively form on the surface of porous carbon. If heat treatment temperature is higher than 1200 DEG C, the structure of porous carbon is easily broken.Simultaneously as the performance of ORR according to 600 DEG C extremely Heat treatment temperature in the range of 1200 DEG C and change, therefore can be adjusted according to the required activity of base metal class catalyst is appropriate Heat treatment condition.Later by description according to the variation of the catalytic activity of heat treatment condition.
After thermally treated mixture, thermally treated mixture is added in into acid solution, and can be by gained Mixture is stirred.The process is carried out to remove inactive transistion metal compound.
Stirring thermally treated mixture in an acidic solution can include adding in thermally treated mixture to concentration For in 0.1M or higher mineral acid solution and stir gained mixture.The type of mineral acid solution can include 0.5M H2SO4Solution, but it is not limited to this.
Meanwhile the concentration of acid solution can be 0.1M or bigger.If the concentration of acid solution is less than 0.1M, Ke Nengnan Fully to remove inactive transistion metal compound.Therefore, if it is desirable to the concentration of acid solution can be suitably controlled.
After the whipping process, agitated mixture can be washed and be dried.The process can be included in decompression It is lower continuously to wash mixture using distilled water, until gains have neutral pH, then dry washed mixture.
Meanwhile after agitated mixture and dry washed mixture is washed, pass through washing and drying process The solid powder of acquisition can be further in ammonia (NH3) be heat-treated in gas atmosphere.In general, the carbon netting gear of porous carbon is defective. When introducing nitrogen into the defects of porous carbon, catalytic activity can further improve.
The process can be included in ammonia atmosphere is heat-treated about 5 at a temperature of about 600 to 1200 DEG C by solid powder To 60 minutes.
If heat treatment temperature is less than 600 DEG C, the surface of base metal class catalyst may not effectively adulterate nitrogen. If heat treatment temperature is higher than 1200 DEG C, the structure of porous carbon is easily broken.In addition, if heat treatment time is less than 5 minutes, Then nitrogen is not adulterated on the surface of base metal class catalyst fully.If heat treatment time is more than 60 minutes, base metal The structure of class catalyst is easily broken.Therefore, it is necessary to suitably adjust heat treatment temperature and heat treatment time effectively to lead nitrogen Enter the surface of porous carbon.
Hereinafter, the variation of the catalytic activity according to heat treatment condition is described with reference to the accompanying drawings.It will be based on following experiment The heat treatment condition in operation 120 and 140 is more fully described.
Figure 14 is the figure for representing the ORR results relative to heat treatment condition.
Figure 14 is shown using 0.5M oxygen saturations H2SO4Solution and load capacity are 815 μ g/cm2Base metal class catalyst The ORR results of the tenth to the 13rd sample measured at 1600 rpm.
In this respect, the tenth to the 13rd sample is the base metal class catalyst sample using FePC, and in difference Heat treatment condition under be heat-treated.Particularly, the tenth sample is heat-treated 60 minutes at 900 DEG C in argon gas atmosphere Base metal class catalyst sample.Tenth a sample is to be heat-treated 60 minutes in argon gas atmosphere at 900 DEG C and then at 950 DEG C The base metal class catalyst sample of 15 minutes is further heat-treated in ammonia atmosphere.12nd sample is in argon gas atmosphere The base metal class catalyst sample of 60 minutes is heat-treated at 1050 DEG C.13rd sample is in argon gas atmosphere at 1050 DEG C 60 minutes base metal class catalyst samples for being then further heat-treated 15 minutes in ammonia atmosphere at 950 DEG C of middle heat treatment Product.
As analyzed based on the curve graph of Figure 14 in -3mA/cm2Lower measurement it is half wave potential as a result, can be confirmed 900 The tenth sample being heat-treated at DEG C has better catalytic activity than the 12nd sample being heat-treated at 1050 DEG C.Meanwhile base The ratio of half wave potential between the comparison of half wave potential between the tenth and the tenth a sample and the 12nd and the 13rd sample It can also relatively confirm, by being further heat-treated base metal class catalyst in ammonia atmosphere, catalytic activity obtains further It improves.
The method of the base metal class catalyst to manufacturing this exemplary implementation is described above.Below In, the base metal class catalyst prepared as described above is effectively introduced into the item in the electrode structure of fuel cell by description Part.
Meanwhile before description condition, it is thus necessary to determine that according to the base metal class catalyst of exemplary implementation whether With 4-e paths.If base metal class catalyst has 4-e paths, water (H is generated by side reaction2O).If however, Base metal class catalyst has 2-e paths, then generates hydrogen peroxide (H by side reaction2O2), thus reduce catalyst effect Rate.Therefore, the analysis result of half-cell is described below to determine whether base metal class catalyst has 4-e paths.
Half-cell analysis design is as follows.
First, 2ml ethyl alcohol and 10 μ are dispersed in by being ultrasonically treated 30 minutes base metal class catalyst by 10mg synthesis L, in the mixed solution of 5 weight %Nafion solution.Herein, using by the way that the porous carbon with anchored site is urged with FePC The base metal class catalyst sample that agent precursor is doped and prepares calculates anti-as base metal class catalyst sample Answer involved electron number.Hereinafter, for convenience, it can will pass through with anchored site porous carbon and FePC The base metal class catalyst sample that catalyst precarsor is adulterated and prepared is known as N-Phth.
Solution coating prepared by 16 μ l on the polished glass carbon of a diameter of 5mm and is dried at room temperature for, and on Drying process is stated to be repeated once.
It connects the electrode to rotating disk electrode (r.d.e) and immerses 0.5M oxygen saturations H2SO4To measure ORR in solution.By linear Voltammetry (LSV) is scanned from 1.0 to 0.1V and carry out cyclic voltammetries (CV) up to can with the 20 of the sweep speed of 10mV/s cycles The voltage of inverse hydrogen electrode (RHE) reaches 1.0V from 0.05V.In this experiment by electrode rotating speed from 400rpm adjust to The Koutecky-Levich figures shown in Figure 15 and Figure 16 are derived while 2500rpm, and use Koutecky-Levich The end value of figure come calculate reaction involved in electron number.
Following equation can be used to calculate the electron number involved in reaction.
Equation 1
Equation 2
Equation 3
In equation 1 to 3, jkFor power current, JLFor carrying current, w is rotating speed, and F is Faraday constant, C0For O2It is dense Degree, DOFor O2Diffusion coefficient, v are viscosity.
According to as the non-of the exemplary implementation involved in the reaction of equation 1 to 3 and Koutecky-Levich figure calculating The electron number of precious metal based catalysts sample is 3.95 under 0.7V.
Based on experimental result, can be confirmed has 4-e paths according to the base metal class catalyst of exemplary implementation. In other words, according to the base metal class catalyst of exemplary implementation by eliminating unnecessary side reaction and with high catalysis Activity.
Hereinafter, condition description base metal class catalyst being effectively introduced into the electrode structure of fuel cell, In other words, it will describe to derive the item for realizing optimization fuel cell according to the base metal class catalyst of exemplary implementation The EXPERIMENTAL EXAMPLE of part.
For this purpose, it assembles monocell after membrane electrode assembly is manufactured and analyzes the performance of monocell.
The process for manufacturing membrane electrode assembly and the process for assembling monocell are as follows.
First, the base metal class catalyst solution according to exemplary implementation is prepared.More specifically, 50g is passed through It is doped with the porous carbon of anchored site and the base metal class catalyst of FePC preparation is dispersed in the 5 weight % of 5ml In the mixed solution of Nafion solution and isopropanol 30 minutes to prepare base metal class catalyst solution.
In addition, the material as the anode for being used to form membrane electrode assembly, platinum catalyst solution are prepared as follows.By 50mg platinum Catalyst is dispersed in the mixed solution of the 5 weight %Nafion solution of 0.2ml distilled water, 5ml isopropanols and 428.6mg 30 points Clock is to prepare platinum catalyst solution.
It is by the method for catalyst coated base material (CCS) and catalyst coated membrane (CCM) that base metal class catalyst is molten Liquid is coated on by manual spray on the electrode surface that area is 1.5cm × 1.5cm.Then, by with the torque of 25kgf*cm It fastens to assemble single battery.
More specifically, base metal class catalyst solution is coated on carbon paper (SGL 35BC) by CCS methods, pass through Base metal class catalyst solution is coated on perfluoro sulfonic acid membrane (Nafion 211) by CCM methods.Meanwhile even if pass through CCS Method is coated, in 70kgf/cm2Pressure under, the hot pressing of 1 minute is carried out at 125 DEG C.In an identical manner, platinum is urged Agent solution coating is on carbon paper and Nafion membrane.In this way, by 0.2mgpt/cm2Platinum catalyst be supported on anode, By 0.5 to 3mg/cm2Base metal class catalyst be supported on cathode.
Next, the performance of monocell is analyzed under the following conditions.
It is as follows for analyzing the condition of monocell performance for being usually applied to Figure 17 to Figure 20.First, monocell is 100% Maintain supply hydrogen and air (so that the amount of hydrogen and air is respectively simultaneously within 2 hours with open-circuit voltage at 65 DEG C under humidity 1.5 times of its stoichiometry and 2 times) after measure monocell performance.It will be described in further detail later and control the process The method of condition.
First, being used to prepare the best spraying method of monocell will be described with reference to Figure 17.
Figure 17 is the performance change figure represented relative to spraying method monocell.It is prepared Figure 17 shows CCS methods are used MEA monocells compared with the performance between the MEA monocells prepared using CCM methods.Herein, by 0.2mgpt/cm2Platinum urge Agent is supported on anode, by 0.5mg/cm2N-Phth be supported on cathode.Meanwhile Nafion in solution used during spraying Mass ratio with catalyst is 1:1.5.
With reference to Figure 17, it can be confirmed that the current density and power density that are obtained under same potential by CCM methods are higher than The current density and power density obtained by CCS methods.
In general, current density higher under same potential shows higher catalytic activity, it is higher under same potential Power density shows better battery performance.Therefore, it can be confirmed that the monocell ratio obtained by CCM methods passes through CCS methods The monocell of acquisition has better performance.
Next, by with reference to Figure 18 describe for manufacture monocell catalyst solution best ratio of components.
Figure 18 is represented relative to added to the Nafion ionomers in catalyst solution and base metal class catalyst Mass ratio, the figure of the performance change of monocell.Herein, by 0.2mgpt/cm2Platinum catalyst be supported on anode, by 0.5mg/ cm2N-Phth be supported on cathode.CCM methods are used as spray coating method simultaneously.
The the 14th to the 18th sample used in this experiment is N-Phth catalyst samples.It is using according to embodiment party In the preparation of the monocell of the base metal class catalyst of case, by by base metal class catalyst and Nafion ionomers and second Alcohol mixes to prepare catalyst solution.In order to find out the optimal proportion of base metal class catalyst, in the 14th to the 18th sample The different quality ratio of Nafion ionomers and N-Phth catalyst is used in product.Hereinafter, for convenience, by catalyst Nafion ionomers and the mass ratio of non-ionic catalysis agent in solution preparation are known as Nafion and catalyst ratio (NCR).Pass through NCR is adjusted to 1.5 to prepare the 14th sample, the 15th sample is prepared by the way that NCR is adjusted to 2, by the way that NCR is adjusted The 16th sample is prepared for 2.5, the 17th sample is prepared by the way that NCR is adjusted to 3, is made by the way that NCR is adjusted to 3.5 Standby 18th sample.
The figure is explained in a manner of identical with Figure 17.It can be confirmed that monocell shows optimum performance when NCR is 2.5. It has been confirmed that due to the wider surface area of catalyst, need relatively great amount of Nafion ionomers that basis is efficiently used The base metal class catalyst of exemplary implementation.If on the contrary, NCR be more than 2.5, the penalty of monocell.Therefore, It can be confirmed that excessive Nafion ionomers may interrupt the supply of oxygen, so as to deteriorate the performance of monocell.
Next, the optimum catalyst load capacity needed for monocell will be prepared with reference to Figure 19 descriptions.
Figure 19 is the figure of the performance change for the monocell for representing the load capacity relative to catalyst.Herein, by 0.2mgpt/ cm2Platinum catalyst be supported on anode, the catalyst solution that NCR is 2.5 is loaded on cathode by CCM methods.
The the 19th to the 22nd sample used in this experiment is N-Phth catalyst samples.In order to find out optimised quantity Base metal class catalyst, the amount of catalyst to being supported on cathode is changed in monocell preparation.Passing through will Catalyst loadings are adjusted to 0.5mg/cm2To obtain the 19th sample.By adjusting catalyst loadings to 1.0mg/cm2 To obtain the 20th sample.By adjusting catalyst loadings to 1.5mg/cm2To obtain the 20th a sample.By that will urge Agent load capacity is adjusted to 3.0mg/cm2To obtain the 22nd sample.
The figure is explained in a manner of identical with Figure 17.It has been confirmed that work as catalyst loadings from 0.5mg/cm2It increases to 3.0mg/cm2When, the performance of monocell improves.This is because on the surface according to the base metal class catalyst of embodiment The hole of a diameter of 20nm formed or more significantly reduces resistance to mass tranfer.
Next, by being manufactured with reference to Figure 20 descriptions by using according to the base metal class catalyst of exemplary implementation Monocell durability test result.
Figure 20 is the figure for the test result for representing monocell durability.Herein, by 0.2mgpt/cm2Platinum catalyst load On anode, by 3.0mg/cm2N-Phth catalyst be supported on cathode.In this respect, NCR is 2.5 base metal class Catalyst solution is supported on by CCM methods on cathode.
First, the initial performance of monocell is measured, as a result as shown in G1.Then, 0.6V between 1.0V in 50mV/s After lower 1500 cycles, the performance of monocell is measured, as a result as shown in G2.
The current density based on measurement can be confirmed, activity reduces about 2.2% under 0.6V.Therefore, use can be confirmed Excellent durability is had according to the monocell of the base metal class catalyst preparation of embodiment.
The fuel electricity for being derived according to exemplary implementation and realizing that base metal class catalyst material optimizes has been described The EXPERIMENTAL EXAMPLE of the condition in pond.
The base metal class catalyst prepared according to the above method and the fuel cell manufactured using the catalyst, pass through tune The condition of whole manufacturing process forms active site on the larger hole surface only in porous carbon pores.Therefore, reactant is in reality Active site is provided easy access in the drive environment on border, and can more effectively utilize active site.
Hereinafter, the position that active site is described with reference to Figure 21 to Figure 23 is utilized to improving active site The influence of rate.
Figure 21 is the figure for the reaction for representing the reactant according to active site position.Figure 22 and Figure 23 is that explanation is opposite In the figure of active site position ORR results and the performance change of monocell.
If active site A is formed on the second hole H2 in the ultra-fine hole shown in the left figure such as Figure 21, reactant Active site A cannot be had easy access to, therefore the function of active site A cannot be efficiently performed.
On the contrary, in the base metal class catalyst sample according to embodiment, active site A is formed in micropore On first hole H1, as shown in the right figure of Figure 21.Therefore, the function of active site A can be efficiently performed.
Figure 22 is shown using 0.5M oxygen saturation sulfuric acid (H2SO4) solution, load capacity is 815 μ g/cm2Base metal class Catalyst and load capacity are 16 μ gpt/cm240 weight %Pt/C measure the 23rd to the 25th sample at 1600 rpm ORR results.In the 23rd sample, active site, but also the also shape in the second hole are not only formed in the first hole Into active site.24th sample is prepared, and by using platinum commonly used in the art by using N-Phth The 25th sample of catalyst preparation.
Figure 23 shows that the performance using the monocell of the 23rd and the 24th sample preparation keeps single at 65 DEG C Battery is supplied simultaneously after hydrogen and air (so that the amount of hydrogen and air is 1.5 times and 2 times of its stoichiometry respectively) Performance change.Herein, by 0.2mgpt/cm2Platinum catalyst be supported on anode, by 3.0mg/cm2N-Phth be supported on On cathode, the NCR of the catalyst solution used in spraying process is 2.5.
With reference to figure 22 and Figure 23, electric current in the 23rd sample that active site is formed in ultra-fine hole can be confirmed Voltage drastically declines during density increase.This is because it is difficult to resistance to mass tranfer be caused to increase close to active site.
However, do not decline rapidly, therefore the 24th sample as the current density in the 24th sample increases voltage Product show monocell performance more better than the 23rd sample.
Based on experimental result, can be confirmed by being selectively controlled in the active site formed in the hole of porous carbon Position, by the way that reactant is made to have easy access to the active site in practical drive environment, can more efficiently use catalysis live Property site.
It can be seen from the above description that according to base metal class catalyst and its manufacturing method, by controlling manufacturing process Condition, only form active site on the micropore surface in porous carbon pores, can be by the way that reactant be made to have easy access to reality Active site in drive environment, so as to improve the utilization of active site.
In addition, there is regular texture and relatively the nanoporous carbon structure of macropore by introducing, it can be by reducing film Resistance to mass tranfer in electrode assembly obtains excellent catalyst performance.
In addition, by the way that anchored site is introduced porous carbon surface, it can be by enhancing the interaction with catalyst precarsor To improve catalytic activity.
The description that specific exemplary embodiment of the present invention is presented in front is for the purpose of illustration and description.They It will not can't limit the invention to disclosed precise forms without missing, it is clear that many modifications according to the above instruction All it is possible with variation.Selection exemplary implementation and to be described be specific principle and other in order to explain the present invention Practical application so that others skilled in the art can realize and utilize the present invention various exemplary implementations Scheme and its different selection form and modification.The scope of the present invention is intended to by the appended claims and its equivalent program It is limited.

Claims (19)

1. a kind of base metal class catalyst for fuel cell electrode, including：
Porous carbon with the first hole and second hole smaller than the first hole,
First hole is with about 5 to 100nm aperture and with the inner wall for the active site for introducing base metal class catalyst.
2. the base metal class catalyst according to claim 1 for fuel cell electrode, wherein porous carbon have it In the structure that uniformly connects in three dimensions of the first hole and the second hole.
3. the base metal class catalyst according to claim 1 for fuel cell electrode, wherein the aperture in the first hole It is about 15 to 60nm.
4. the base metal class catalyst according to claim 1 for fuel cell electrode, wherein the base metal The active site of class catalyst is provided in the form of being represented by following formula 1：
Formula 1
MxNy
Wherein x is 0 to 1 integer, and y is 1 to 4 integer, and M is transition metal.
5. the base metal class catalyst according to claim 1 for fuel cell electrode, wherein base metal class is urged The active site of agent is formed by base metal class catalyst precarsor.
6. the base metal class catalyst according to claim 5 for fuel cell electrode, wherein the base metal Class catalyst precarsor has wherein at least one of following form with metal coordination：Phthalocyanine, phthalocyanine tetrasulfonate, eight fourth oxygen Base phthalocyanine, ten hexafluoro phthalocyanines, eight octyloxy phthalocyanines, tetra-tert phthalocyanine, four azepine phthalocyanines, four phenoxy group phthalocyanines, tetra-tert Four-dimethylamino phthalocyanine, four cumylphenoxy phthalocyanines, four pyrido methyl phthalocyanines, tetranitro phthalocyanine, naphthalene phthalocyanine, tetra-tert Naphthalene phthalocyanine, tetraphenylporphines, four pentafluorophenyl group porphyrins, tetramethyl pyridine and porphyrin tetramethyl benzene sulfonate, four-trimethylamino benzene Base porphyrin tetramethyl benzene sulfonate, tetramethyl divinyl porphines dipropionic acid, four pyridyl group porphines, octaethylporphyrin, tetramethoxy Phenyl porphine, tetraphenylporphines tetrabasic carboxylic acid, tetrahydroxy phenyl porphine, tetrasulfonic acid root close phenyl porphine, etioporphyrin (ETIO), 1,10- phenanthrene and cough up Quinoline, 1,10- phenanthroline -5,6- diketone dimethyl -1,10- phenanthroline, dimethyl -1,10- phenanthroline, dimethoxy -1,10- are luxuriant and rich with fragrance Cough up quinoline, amino -1,10- phenanthroline, methyl-1,10- phenanthroline, dihydroxy -1,10- phenanthroline, tetramethyl -1,10- phenanthroline, Chloro- 1,10- phenanthroline, two chloro- 1,10- phenanthroline, nitro -1,10- phenanthroline, bromo- 1,10- phenanthroline, four bromo- 1,10- are luxuriant and rich with fragrance Cough up quinoline, pyrazine simultaneously [1,10] phenanthroline, diphenyl -1,10- phenanthroline, dimethyl diphenyl -1,10- phenanthroline, ethylidine first It is two propoxy- of acyl group (hydroxyl trimethyl tetradecyl base) trimethyl porphines, two propoxy- of diethylene tetramethyl porphines, double Two propoxy- of ((amino carboxyethyl) is thio) ethyl tetramethyl porphines, dihydro dihydroxy tetramethyl divinyl porphines dipropionic acid Lactone, two propoxy- of ethylidine (14 carbon trialkenyl of hydroxyl trimethyl) tetramethyl porphines, carboxyl ethylidine carboxyethyl dihydro Bis- (methylol) tetramethyl porphines dicarboxylic acids compounds, (dimethylbenzimidazole base) cyanocobalamin amide, the big rings of Ke Disi, Big ring and the big rings of DOTA.
7. the base metal class catalyst according to claim 6 for fuel cell electrode, wherein metal include being selected from At least one of iron (Fe), cobalt (Co), manganese (Mn), nickel (Ni) and chromium (Cr) transition metal.
8. the base metal class catalyst according to claim 5 for fuel cell electrode, wherein based on porous carbon Total weight, base metal class catalyst precarsor include the transition metal of about 1 to 50 weight %.
It is led 9. the base metal class catalyst according to claim 5 for fuel cell electrode, wherein porous carbon have Enter the anchored site of the hole surface of porous carbon, to enhance the interaction between porous carbon and base metal class catalyst precarsor.
10. a kind of manufacturing method of base metal class catalyst for fuel cell electrode, the method includes：
Porous carbon is mixed with base metal class catalyst precarsor；
Mixture is heat-treated at a temperature of about 600 to 1200 DEG C；
Thermally treated mixture is stirred in an acidic solution；And
It washs and dries agitated mixture.
11. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, wherein Porous carbon has the first hole and second hole smaller than the first hole, and in the mixing of porous carbon and base metal class catalyst precarsor In the first hole have about 5 to 100nm aperture.
12. the manufacturing method of the base metal class catalyst according to claim 11 for fuel cell electrode, wherein First hole has about 15 to 60nm aperture.
13. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, is also wrapped It includes in ammonia (NH3) it is dry at a temperature of about 600 to 1200 DEG C in gas atmosphere after, the solid powder of acquisition is heat-treated About 5 to 60 minutes.
14. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, is also wrapped It includes by ammonia (NH3) porous carbon is heat-treated at a temperature of about 600 to 1200 DEG C in gas atmosphere about 5 to 60 minutes and porous Anchored site is formed on the hole surface of carbon.
15. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, wherein In the mixing of porous carbon and base metal class catalyst precarsor, base metal class catalyst precarsor have it is wherein following in extremely A kind of few form with metal coordination：Phthalocyanine, phthalocyanine tetrasulfonate, eight butoxy phthalocyanines, ten hexafluoro phthalocyanines, eight octyloxy phthaleins Cyanines, tetra-tert phthalocyanine, four azepine phthalocyanines, four phenoxy group phthalocyanines, four-dimethylamino of tetra-tert phthalocyanine, four cumylphenoxies Phthalocyanine, four pyrido methyl phthalocyanines, tetranitro phthalocyanine, naphthalene phthalocyanine, tetra-tert naphthalene phthalocyanine, tetraphenylporphines, four pentafluorophenyl groups Porphyrin, tetramethyl pyridine and porphyrin tetramethyl benzene sulfonate, four-trimethylamino phenyl porphyrin tetramethyl benzene sulfonate, tetramethyl two Vinyl porphines dipropionic acid, four pyridyl group porphines, octaethylporphyrin, tetramethoxy phenyl porphine, tetraphenylporphines tetrabasic carboxylic acid, four Hydroxy phenyl porphines, tetrasulfonic acid root close phenyl porphine, etioporphyrin (ETIO), 1,10- phenanthroline, 1,10- phenanthroline -5,6- diketone diformazans Base -1,10- phenanthroline, dimethyl -1,10- phenanthroline, dimethoxy -1,10- phenanthroline, amino -1,10- phenanthroline, methyl - 1,10- phenanthroline, dihydroxy -1,10- phenanthroline, tetramethyl -1,10- phenanthroline, chloro- 1,10- phenanthroline, two chloro- 1,10- are luxuriant and rich with fragrance Cough up quinoline, nitro -1,10- phenanthroline, bromo- 1,10- phenanthroline, four bromo- 1,10- phenanthroline, pyrazine simultaneously [1,10] phenanthroline, hexichol Base -1,10- phenanthroline, dimethyl diphenyl -1,10- phenanthroline, ethylidine formoxyl (hydroxyl trimethyl tetradecyl base) front three Two propoxy- of base porphines, two propoxy- of diethylene tetramethyl porphines, bis- ((amino carboxyethyl) is thio) ethyl tetramethyls Two propoxy- of porphines, dihydro dihydroxy tetramethyl divinyl porphines dipropyl acid lactone, ethylidine (14 carbon of hydroxyl trimethyl Trialkenyl) two propoxy- of tetramethyl porphines, bis- (methylol) the tetramethyl porphines dicarboxylics of carboxyl ethylidine carboxyethyl dihydro Object, (dimethylbenzimidazole base) cyanocobalamin amide, the big rings of Ke Disi,Big ring and the big rings of DOTA.
16. the manufacturing method of the base metal class catalyst according to claim 15 for fuel cell electrode, wherein Metal can include at least one transition metal selected from iron (Fe), cobalt (Co), manganese (Mn), nickel (Ni) and chromium (Cr).
17. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, wherein In the mixing of porous carbon and base metal class catalyst precarsor, the total weight based on porous carbon, before base metal class catalyst Body includes the transition metal of about 1 to 50 weight %.
18. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, wherein Heat treatment of the mixture at a temperature of about 600 to 1200 DEG C is included in inert gas atmosphere at a temperature of 600 to 1200 DEG C The heat treatment of about 10 to 300 minutes is carried out to mixture.
19. the manufacturing method of the base metal class catalyst according to claim 10 for fuel cell electrode, wherein Thermally treated mixture is stirred in an acidic solution to include adding in thermally treated mixture to a concentration of 0.1M or higher Acid solution in and stir gained mixture.
CN201710744032.6A 2016-12-21 2017-08-25 Non-noble metal catalyst and process for producing the same Active CN108232205B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160175354A KR101894920B1 (en) 2016-12-21 2016-12-21 Non-noble metal based catalyst and method of manufacturing the same
KR10-2016-0175354 2016-12-21

Publications (2)

Publication Number Publication Date
CN108232205A true CN108232205A (en) 2018-06-29
CN108232205B CN108232205B (en) 2022-10-11

Family

ID=62251792

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710744032.6A Active CN108232205B (en) 2016-12-21 2017-08-25 Non-noble metal catalyst and process for producing the same

Country Status (4)

Country Link
US (2) US10615424B2 (en)
KR (1) KR101894920B1 (en)
CN (1) CN108232205B (en)
DE (1) DE102017110494A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112840478A (en) 2018-11-07 2021-05-25 株式会社Lg化学 Lithium secondary battery
WO2020096331A1 (en) * 2018-11-07 2020-05-14 주식회사 엘지화학 Lithium secondary battery
CN110707332B (en) * 2019-09-29 2022-06-21 中国石油大学(华东) Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst
KR20210115529A (en) * 2020-03-13 2021-09-27 현대자동차주식회사 Method of manufacturing a catalyst ink with removed exsoluted transition metal for a fuel cell
WO2022196913A1 (en) * 2021-03-16 2022-09-22 한양대학교에리카산학협력단 Monatomic catalyst structure and preparation method thereof
CN117363055A (en) * 2023-10-16 2024-01-09 甘肃省交通规划勘察设计院股份有限公司 Porphyrin modified graphene and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1960042A (en) * 2006-10-13 2007-05-09 北京工业大学 Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method
JP2008243697A (en) * 2007-03-28 2008-10-09 Ricoh Co Ltd Direct alcohol type fuel cell, and anode catalyst
CN101401237A (en) * 2006-03-14 2009-04-01 株式会社科特拉 Fuel cell electrode catalyst with improved noble metal utilization efficiency, method for manufacturing the same, and solid polymer fuel cell comprising the same
CN103181010A (en) * 2010-10-22 2013-06-26 日产自动车株式会社 Electrocatalyst for solid polymer fuel cell
CN104624154A (en) * 2015-01-23 2015-05-20 南开大学 Preparation method and application of iron-nitrogen co-doped porous carbon sphere material
CN105344369A (en) * 2015-11-30 2016-02-24 北京化工大学 Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof
CN105728009A (en) * 2014-12-12 2016-07-06 中国科学院大连化学物理研究所 Metal/nitrogen/carbon hierarchical porous electrocatalyst, preparation and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10132490B4 (en) 2001-07-03 2007-04-12 Hahn-Meitner-Institut Berlin Gmbh Platinum-free chelate catalyst material for selective oxygen reduction and process for its preparation
DE102005033938B4 (en) 2004-12-06 2007-09-13 Institut für Niedertemperatur-Plasmaphysik e.V. an der Ernst-Moritz-Arndt-Universität Greifswald Process for the plasma-supported support, activation and stabilization of catalysts by treatment with low-temperature plasma and use of the catalysts for the reduction of hydrogen peroxide and / or nitric acid in fuel cells
KR101473319B1 (en) 2007-10-16 2014-12-16 삼성에스디아이 주식회사 Hierarchical mesoporous carbon, manufacturing method thereof, and fuel cell using the same
KR100987498B1 (en) * 2008-07-24 2010-10-13 고려대학교 산학협력단 ???? carbon-supported electrode catalysts in proton exchange membrane fuel cell and method for manufacturing the same
JP6240771B2 (en) 2013-11-29 2017-11-29 エルジー・ケム・リミテッド Fuel cell and manufacturing method thereof
JP2016203133A (en) * 2015-04-28 2016-12-08 ダイハツ工業株式会社 Oxygen reduction catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101401237A (en) * 2006-03-14 2009-04-01 株式会社科特拉 Fuel cell electrode catalyst with improved noble metal utilization efficiency, method for manufacturing the same, and solid polymer fuel cell comprising the same
CN1960042A (en) * 2006-10-13 2007-05-09 北京工业大学 Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method
JP2008243697A (en) * 2007-03-28 2008-10-09 Ricoh Co Ltd Direct alcohol type fuel cell, and anode catalyst
CN103181010A (en) * 2010-10-22 2013-06-26 日产自动车株式会社 Electrocatalyst for solid polymer fuel cell
CN105728009A (en) * 2014-12-12 2016-07-06 中国科学院大连化学物理研究所 Metal/nitrogen/carbon hierarchical porous electrocatalyst, preparation and application thereof
CN104624154A (en) * 2015-01-23 2015-05-20 南开大学 Preparation method and application of iron-nitrogen co-doped porous carbon sphere material
CN105344369A (en) * 2015-11-30 2016-02-24 北京化工大学 Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ERIC PROIETTI 等: "Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells", 《NATURE COMMUNICATIONS》 *

Also Published As

Publication number Publication date
KR20180072122A (en) 2018-06-29
CN108232205B (en) 2022-10-11
US10615424B2 (en) 2020-04-07
US20200194805A1 (en) 2020-06-18
US11145872B2 (en) 2021-10-12
US20180175395A1 (en) 2018-06-21
DE102017110494A1 (en) 2018-06-21
KR101894920B1 (en) 2018-09-04

Similar Documents

Publication Publication Date Title
CN108232205A (en) Base metal class catalyst and its manufacturing method
Qu et al. Stepwise pyrolysis treatment as an efficient strategy to enhance the stability performance of Fe-NX/C electrocatalyst towards oxygen reduction reaction and proton exchange membrane fuel cell
US20210202955A1 (en) Carbon dioxide reduction electro catalysts prepared for metal organic frameworks
Jiang et al. A cobalt–nitrogen complex on N-doped three-dimensional graphene framework as a highly efficient electrocatalyst for oxygen reduction reaction
Qiao et al. Effect of KOH concentration on the oxygen reduction kinetics catalyzed by heat-treated co-pyridine/C electrocatalysts
CN111146457B (en) Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound
Morozan et al. Electrochemical performance of annealed cobalt–benzotriazole/CNTs catalysts towards the oxygen reduction reaction
Bezerra et al. Novel carbon-supported Fe-N electrocatalysts synthesized through heat treatment of iron tripyridyl triazine complexes for the PEM fuel cell oxygen reduction reaction
Liu et al. High-surface-area CoTMPP/C synthesized by ultrasonic spray pyrolysis for PEM fuel cell electrocatalysts
Roncaroli et al. Cobalt and iron complexes with N-heterocyclic ligands as pyrolysis precursors for oxygen reduction catalysts
EP0512713A1 (en) Catalyst material
CN110201662B (en) Electrochemical preparation method of carbon-supported monatomic metal catalyst
CN112968185B (en) Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure
Snitkoff et al. Imidazole decorated reduced graphene oxide: A biomimetic ligand for selective oxygen reduction electrocatalysis with Metalloporphyrins
CN114293223B (en) Method for preparing superfine cerium dioxide supported metal monoatomic catalyst from cluster-based framework material
CN102451727A (en) M/N-C catalyst and preparation and application thereof
Kiros Metal porphyrins for oxygen reduction in PEMFC
Du et al. Applications of RDE and RRDE methods in oxygen reduction reaction
CN109155417A (en) Battery electrode, the composition and battery of the catalyst layer for battery electrode
CN105594035A (en) Catalyst particles, electrocatalyst using the same, electrolyte membrane-electrode assembly, and fuel cell using the catalyst particles
Qiao et al. Carbon-supported co-pyridine as non-platinum cathode catalyst for alkaline membrane fuel cells
CN108232208A (en) Method for the mixed catalyst of fuel cell and for manufacturing it
CN103706375B (en) Preparation method for the PtFe/C catalyst of Proton Exchange Membrane Fuel Cells
Danilovic et al. Effect of substitution with Cr3+ and addition of Ni on the physical and electrochemical properties of Ce0. 9Sr0. 1VO3 as a H2S-active anode for solid oxide fuel cells
Xu et al. Nitrogen/sulfur co-doped non-noble metal material as an efficient electrocatalyst for the oxygen reduction reaction in alkaline media

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant